Azo dyestuffs



Patented June 1, 1937 PATENT OFFICE 2,082,156 1520 nYEs'rU'FFs Friedrich Felix and Wilhelm Huber, Basel, Switzerland, assignors. to

the firm of Society of Chemical Industry in Basle, Basel, Switzerland No Drawing.

Original application March 21,

1935, Serial No. 12,299. Divided and this application October 15,

1935, Serial No. 45,164.

In Switzerland March 24, 1934 14 Claims.

This application is a division of our application for patent Ser. No. 12,299, filed in the U. S. A. on March 21, 1935, and in Switzerland on March invention relates to the manufacture of dyestuffs by coupling a diazotized aromatic amine of the generalformula in which Y stands for a sulfone radical of :the general formula SO2-CH2'R wherein R represents H, alkyl or phenyl, and X stands fora nitrogenous group which is linked with its nitrogen atom to the organic radical, such as an NOz-group, an x alkyl I (R representing hydrogen, alkyl, aralkyl oraryl),

e. g. an acidylamino-group, such as-an acetylaminoor benzoylamino-group, with a coupling component of the generalformula in which A'stands for a nucleus of, the benzene series which may or may not be substituted, and R1 and R2 stand for hydrogen, a1kyl,-a ryl or aralkyl radicals, the conditions of coupling being chosen in such a manner that the R: N -group 11:

literature cf. British Patent 26,336/ 1910 claim 1,

substituted'alkyl radicals, for example alkyl radicals substituted by halogen, such as, for example, chloro-, bromoor iodo-ethyl radicals, alkyl radicals substituted byOH-groups, such as hydroxyethyl-, hydroxypropyl-, hydroxybutylor dihy droxy-propylene radicals, further the ethers and esters; thereof, such as methoxyethylor acetoxyethylor ethylsulfuric acid radicals, furtheralso alkylcarboxylic acid radicals and their derivatives, such as propionic acid radicals or propionic ester radicals or propionic acid amide radicals, or the radicals of ethylnitrile or ethylsulfocyanide. The

Larylor aralkyl-radicals R1 and R2 may also be substituted in the aromatic nucleus.

As products of the general formula there may be named, for instance, 1-amino-4- nitrobenzene-Z-methyl- (or 2-ethylor 2- benz'ylor Z-hydroxyethyl-or 2-hydroxybenzylor Z-carboxymethylor carboxymethylester methyl)- sulfone, the corresponding 1-amino-4-nitro-5- chlorobenzene-2-alkylsulfone, the corresponding l-amino-i-nitro 6 chlorobenzene 2 alkylsulfone, the correspondingsulfones in. which the chlorine is exchanged for bromine or iodine, and 1-amino-4,6-dinitrobenzene 2 methylsulfone, further the 1-amino L-acetylaminophenyl- 2 methylsulfone, the l-amino 4 acetylaminophenyl-Z-ethylsulfone, the 1-amin0-5-chloro-4- acetylaminophenyl-2-methylsu1fone, the l-am- .ino-4-benzoylaminophenyl-Z-methylsulfone, the l-amino-4- (4-methoxy) -benzoylaminophenyl-2- methylsulfone, the 1-amino-4-(4'-chloro)-benzoylaminophenyl-Z-methylsulfone, the 1-amino 4-benzoylaminophenyl-2-ethylsulfone, the l-amino-4-benzolaminophenyl-2-benzylsulfone, the 1- amino 4-phenoxyacetylaminophenyl-2-methylsulfone, the,1-amino-4(4'-ethoxy) -phenoxyacet ylaminophenyl 2 methylsulfone, the 1 amino 4(2' methyl) phenoxyacetylamiophenyl- 2-ethylsu1fone, the 1-amino-4-phenyl-acetylaminophenyl-Z-methylsulfone, the 1-amino-4-dimethylamino-phenyl=2-ethylsulfone, the l-amino-4-diethylaminophenyl 2 ethylsulfone, and thelike. a

causes coupling means the coupling of the component in neutral or acid medium usual for aromatic amines. However, if thearomatic nucleus A contains one or more phenolic OH-groups,

only coupling in acid medium comes into consideration. But, as is well known, the selection of the coupling conditions in such a manner that the amino group of a coupling component isthe group which causes coupling does not present a problem to the expert, but a known measure.

The dyestuffs thus producedcan be converted intoother valuable products .by treatingthem with suitable 'reducing'agents so. that the'nitrogroup of thediazo-component' is reduced, and, if desired, either acylating orialkylating the new amino-group by means of the usual agents, ,or converting the reduced body intoother dyestuffs by diazotizing the amino-group and coupling with suitable coupling components.

The new dyestuffs correspond therefore to the general formula in which X stands for a nitrogenous group which is linked with its nitrogen atom to the aromatic nucleus, such as anNOz-group; an NHz-group, an

alkyl N group, an N-CR1-group,

I I H alkyl (R1 representing hydrogen, alkyl, aralkyl or aryl) i. e. an acetylamino or benzoylamino-group,a phenylacetylamino or phenoxyacetyl a m i n o group, Y stands for a sulfone radical of the general formula SO2CH2R (R representing H, alkyl or aryl), A for an aromatic nucleus of the benzene series, and B for an amino-group wherein R1 and R2 stand for H, alkyl, aryl or aralkyl, which amino-group stands in ii-position to the -N=N-group.

The dyestuffs thusv obtained are red to green powders, which are excellently suitable for dyeing textiles of various kinds, for example wool, silk, artificial silk, cellulose, particularly esters and ethers thereof, for example acetylcellulose and other conversion products 'of cellulose, such as nitrocellulose etc. The dyestuffs are also suit able for dyeing lacquers, varnishes and plastic masses, particularly nitrocellulose and phenolformaldehyde lacquers. They dye these products the same tints as the textiles; unsulfonated dye- 75 stuffs are particularly suited for this purpose;

They can be used as intermediate products for the manufacture of further dyestuffs. Whereas the .sulfonated dyestuffs are particularly valuable for dyeing and printing wool and for printing acetate artificial silk, the non-sulfonated dyestuffs, when brought-into suitable form or suspended in a suitable medium, have pronounced affinity for cellulose esters and ethers particular- 1y acetate artificial silk. Besides dyestuffs which dye red, violet and brown tints there can, by a suitable choice of the coupling components be obtained dyestuffs which have the valuable property to dye acetate artificial silk blue tints capable of discharge.

Among the components which come into question for making wool dyestuffs there are suitable, quite generally, aminoor amino-hydroxy-compounds of the benzene series which are capable of coupling, or sulfonic acids of such compounds, particularly alkylaniline-sulfonic acids, for instance ethylbenzylaniline-sulfonic acid.

These dyestuffs correspond therefore to the general formula in which X; A, B and B have the significations indicated above, and in-which the aromatic radical A carries at least one sulfo-group. They are dark powders dissolving in water with addition of alkalies to orange, to red, to violet and blue solutions and dyeing wool from an acid bath similar tints of good fastness properties.

For, dyeing acetate artificial silk suitable dyestuffs are, in particular, obtained when such diazo-components of the kind in question are used as contain no sulfuric acid groups and the coupling components are simple aromatic bases, such as aniline and its homologues and analogues. There may be used therefore aniline, ortho-' or meta-toluidine, para-xylidine, para-cresidirie, 2,5-dihydroxyalkylaminobenzene, also the amines alkylated or hydroxyalkylated in the aminogroup, and those hydroxyalkylated amines the hydroxy-groups of which can be etherified or esterified. The properties of fastness and the tints of the materials dyed with these dyestuffs are, within certain limits, altered by the selection of the substituents. These dyestuffs correspond to the general formula I SO;

in which X, A, B and B. have the signification indicated hereinbefore in the description of the starting materials, and in which the aromatic radical A carries no sulfo-groups. Among these dyestuffs those are'particularly valuable which correspondto the general formula SI 0 2 alkyl in which X, A and B have the signification already indicated.

All these products are dark powders insoluble in water, but dissolving in acetic ester to yellow to red to blue solutions and dyeing acetate artificial silk red toblue tints of good fastness. Among these products those are again particularly valuable in which X standsfor a nitro-group.

Among these products special mention must be made of those products in which the radical A stands for a benzene radical and which correspond to the general formula wherein the alkyl-group of the sulfone radical contains not morethan ,two carbon atoms, A stands for an aromatic nucleus of the benzene series, the

Ri N -group Rz stands in the 4position to the azo-group, R1 standing for alkyl ora hydrogen atom and R2 for alkyl, at least one of the alkyl-groups being.

substituted by such a substituent as does not provoke solubility of the dyestuff in water. Such substituents are inter alia halogen, such as chlorineor bromine, cyanogen, thiocyanogen, OH,

or quite generally the grouping QR3, wherein R3 stands for hydrogen, alkyl or acidyl.

All the above mentioned p-nitro-azio dyestufis in which A corresponds to a radical of the benzene series, are dark powders insoluble in water, but dissolving in acetic ester to violet to blue and green solutions, and dyeing acetate artificial silk from suspension dye-baths violet to blue and green tints.

These non-sulfonated dyestufis, which are sparingly soluble in water, are used for dyeing acetate artificial silk, preferably in finely dispersed form produced by grinding them with dispersing agents, for instance the sulfonated residue from the manufacture of benzaldehyde or turpentine oil and the like, in the presence of Water until a fine paste is produced; or they may be converted in the presence of further quantities of the aforesaid or other auxiliary substances, such as sulfite cellulose waste liquor, by cautiously drying them in a vacuum at a temperature which is not too high, into dry preparations capable of being powdered.

The following examples illustrate the invention, the parts being by weight:-

Example 1 2,os2,15e

The dyestuff is precipitated in the form of a dark powder-. When coupling has :been completed'by the addition of sodium acetate the dyestuff is filtered and washed until neutral.

The dyestuff thus obtained is, when dry, a'dark powder, soluble in organic solvents suchas acetone or ethylacetate to a brilliant blue-red solution. By suitable additions it may be brought into fine dispersion and will then dye acetate artificial silk pure violet red tints. The dyestufl corresponds with the formula When substituting dimethylor diethylaniline for the N-ethyl, N-hydroxyethylaniline there are obtained bluish-reddyestufis.

Scarlet red dyestuffs are obtained when using aniline'as coupling component, the ii-methanesulfonic acid of theaniline then united in known manner with the diazo compound, and the dyestufi saponified. Blue-reddyestulfsare further obtained from thesame diazotizing com ponent, and coupling components, such as 1 C or also N The products from N-hydroxyethylaminobenzene, N-methoxyethylaminobenzene, N-acetoxyethylaminobenzene, N-ethyl-N-acetoxyethylaminobenzene, N-methoxyethyl-, N-acetoxyethylaminobenzene, N (diacetoxyethyl) aminobenzenes are also blue-red dyestuffs; Further, the dyestufis from meta-phenylenediamine, metatoluylenediamine or mono-acetyl-metaphenylenediamine are red to scarlet red products.

. Example 2 I CzHs Also in this case the substitution of dimethylaniline or di-ethylaniline, or also aniline (here over the wmethane-sulfonic' acid) for ethylmethoxyethylaniline leads to red or scarlet red dyestufis I v Enamplee A diazo-solution made from 21.6 parts of 2- amino-5-nitrophenylmethylsulfone is coupled with a solution of 25.3 parts of 2-methoxy-5- methyl-1-[ (di-methoxyethyl) -amino] -benzene in dilute mineral acid. The coupling is finished by the addition of sodium acetate. The dyestufi thus obtained is a dark powder soluble in acetone, ethylacetate or the like to a red-violet solution. In suitable dispersion it dyes acetate artificial silk violet tints. The dyestuff corresponds with the formula Example 4 A diazo-solution made from 21.6 parts of 2- amino-5-nitro-phenylmethylsulfone is coupled with a solution of 19.5 parts of 2-methoxy-5- nieth yl-l-methoxyethyl-aminobenzene in .dilute mineral acid. The coupling 'is 'completed by addition of sodium acetate. The dyestuff thus obtained is a dark powder soluble in acetone, ethyl acetate or the like toa red-violet solution. In suitable dispersion it dyes acetate artificial silk violet tints. The dyestuficorresponds with the formula.

NzN=N v I SIO2CH;

The dyestufi from 2,5-dimethyl-1-aminobenzene dyes nitrocellulose varnishes Bordeaux-red tints.

' Example A diazo-solution made from 21.6 parts of 2- 'amino-5-nitro-phenylmethylsulfone is coupled with a solution of 22.5 parts of 2-methoxy-5- L methyl-b (di-hydroxyethyl) -aminobenzene in di- "lute mineral acid. Coupling is completed by the addition of sodium acetate. The dyestuff thus obtained is a dark powder soluble in acetone, ethyl acetate or the like to a violet solution. In suitable dispersion it dyes acetate artificial silk blue-violet tints. The dyestufif corresponds with the formula In the following table there are listed some other dyestufis obtainable in accordance with this inventiom- Q-gwom-om-o-om Color 0! the Dyeingon D1azo-component Coupling component solution in ethyl acetate artificial acetate silk 1-. 2-amino-5-nitrophenyl Ethylhydroxyethylanllinm Red-violet Red-violet.

methylsulfone. v v 2 do Ethyl-'ethoxy-ethylanlline. Do.

do 2 methoxy 5 -methyl 1 Blue-violet.

' (butyl methoxyethyl) i aminobenzene. 4.-- do Mleiathyl methoxyethylani'-. Red.--.'. Red.

ne. v 5.-- ..do 2,5 dimethoxy 1. (di Blue-violet Blue-violet.

methoxyethyl) amino benzene. 6--- ..do Methyl acetoxyethyl am- Ruby Ruby.

v V I '7. do .1. Di-hydroxyethylaniline..- .do Do.

8.- 2 am no 5 nitrophenyl --do Bordeaux- Bordeaux.

' ethylsulfone. g T 9 2 amino 5 nitrophe do. Re Do.

nyl-beuzylsulfone. 10 2 amino 5-- nitro 6 do gRed-violet Red-violet.

ghlorophenylmethylsul v one. a 11... do 2 methoxy 5 methyl -'1 Violet Violet. (Inethoxyethyl d1 hy I droxypropyl) aminoben I wzene. 12 2 amino 5 nitro phe 2 methoxy 5 methyl l Blue-vi0let Blue-violet.

' nyl-methylsulfonef; (hydroxyethyl-methoxy- I a ethyD-aminobenzene.

13 2 methoxy 5 methyl 1 do Do.

(methoxyethyl --d 1 hy droxypropyl) ammoben zene. 7 l4. 2 methoxy 6 methyl 1 Red-violet Red-violet. ethylaminobenzene. l5 do Allyl-methoxyethylaniline-- Ruby Ruby.

16.-- do Allylethylaniline -do.' Do.

001mg @gag Dyeing on wool 17--- 2- amino -5-acetylamino- Ethylbenzylanillne-sulfonic Orange Orange.

' phenyl-methylsnlfone. acid. 18.; 2-'am1no-5-acetylaminodo -do I Do.

phenyl-benzylsulione.

.T he, formulae of the characteristic the table are the following:

products of.

green solutions and dyeing lacquers and the fiber red to blue tints.

I (17) N -N=N If I 01H; Q0011, s0,

Example 6 10 parts of the dyestuffof Example .2 are stirred with a suitable dispersing agent such as Turkey red oil, sulfite cellulose solution or the sulfonatiori" product of the residue of the benzaldehydemarrufacture to form a uniform paste containing 20 per cent. of dyestuif. timately mixed with 10 parts of water at 50 C.

and so much concentrated soa'p solution as will 1 make the dye-bath a soap solution of 2 per cent. strength. This mixture is diluted with cold wa ter to about 300 parts. Into the emulsion thus made there are entered 1 0 parts of acetate artificial silk yarn which is handled while the bath is heated within hour to "75 C dyeing is continued for hour at this temperature. ,The

goods are them rinsed and brightened as usual.

There is obtained a vivid Bordeaux .reddyei'ng.

What We claim is:-

1. The azo-dyestuffs of the general formula. I

in which R stands-for a member of the group consisting or hydrogen,alky1 and aryl, A for an aromatic nucleus of the benzene series, and B for an amino group standing 'inthe 4''position to the N=N-gro'up, which products are dark powders soluble pyridine to red, violet, blue and 1 part of this-paste is very i-n--.

2. The azo-dyestuifs of the general formula SO -OHz-R 3. 'Ihe'azo-dyestufis of the general formula SOi-alkyl in which A stands ioran aromatic nucleus of the benzene series, and B for an amino-group standing in the 4-position to the -N=N-group, which products are dark powders soluble in pyridine'to red, violet and blue solutions and dyeing lacquers and the fiberred to blue tints.

4..'I'he unsulfonated azordyest'uifs: of .the general formula OHz-OHrO-flh 7 s Oz-alkyl wherein the alkyl-group of the SOz-alkylradiCal does not contain more than, 2 carbon atoms; A

stands for an aromaticnucleus of the benzenestands in the 4-position to the azo-group, R1 meaning amember of the group consisting of hydrogen, alkyl and acidyl, R2 a member of thegroup consisting of hydrogen, alkyl and the group CH2-CH2'O"-'R3, R3 of the latter. group standing for a member of the group consisting of hydrogen, alkyl, and acidyl, which products are dark powders insoluble in water but dissolving in acetic ester to'red'to blue solutions; anddyeing acetate artificial silk from a dye bath containing these produc'ts in'a fine dispersion red toblue tints of good 'fa'stness properties.

5. The unsulfonated azo-dyestuifs of the general formula t alkyl wherein the alkyl-group of the SOs-alkyl radical does I not contain more' than 2 'carbon' atoms, A

stands 'foran aromatic nucleusof the benzene series, and "the group as stands in the 4-position to the azo-group, R1 meaning a member of the group consisting of hydrogen, alkyl and acidyl, which products are dark powders insoluble in water but dissolving in acetic ester to red to blue solutions, and dyeing acetate artificial silk from a dye-bath containing these products in a fine dispersion red to blue tints of ood fastness properties.

6. The unsulfonated azo-dyestufis of the general formula wherein the alkyl-group of the SOs-alkyl radical does not contain more than 2 carbon atoms, A stands for an aromatic nucleus of the benzene series, and the group orn-om-o-m CHr-CHr- O-R -'I..The unsulfonated azod'yestuffs of the general formula I 1 alkyl N=N-A-N P 20OHa S Or-alkyl wherein the alkyl-group of the SOz-alkyl radical does not contain more than 2 carbon atoms, A stands for an aromatic nucleus of the benzene series, and'thegroup alkyl.

" on -on-ro -ons stands in we l-position to the azo-group; which products are dark powders insoluble in water but dissolving in acetic ester to red to blue solutions, and dyeing acetate artificial silk from a dyebath containing these'products ina fine dispersion red to blue tints of good fastne'ss properties.

8. The unsulfonated azo-dyestuifs of the general formula I CH2 CH20R1 N05 I I- ,l A- N H OHPOHQ-QH SOs-alkyl wherein the alkyl-group'of the SOz-alkyl radical does not contain more than 2 carbon atoms, A

stands for an aromatic nucleus of the benzene series, and the group k C Z Hi l Q \OHFOHFOH standsi nthe4 position' to the azo-group, R1

meaning a member of thegroup consisting of hydrogen, alkyl and acidyl, which products are dark powders insoluble in water but dissolving in acetic ester to red to blue solutions, and dyeing acetate artificial silk from a dye-bath containing these products in a fine dispersion red to blue tints of good fastness properties.

9. The unsulfonated azo-dyestuffs of the general formula wherein the alkyl-group of the SOz-alkyl radical does not contain more than 2 carbon atoms, A stands for an aromatic nucleus of the benzene series, and the group CHg-CHz-OH CHg-CHz-OH stands in the 4-position to the azo-group, which products are dark powders insoluble in water but dissolving in acetic ester to red to blue solutions, and dyeing acetate artificial silk from a dye-bath containing these products in a fine dispersion red to blue tints of good fastness properties.

10. The unsulfonated azo-dyestuffs of the general formula OHrCHz-O-OH:

wherein the alkyl-group of the SOz-alkyl radical does not contain more than 2 carbon atoms, A

stands for an aromatic. nucleus of the benzene series, and the group 1 wherein the alkyl-group of the SOz-alkyl radical does not contain more than 2 carbon atoms, A stands for an aromatic nucleus of the benzene series, and the group stands in the 4-position to the azo-group, which products are dark powders insoluble in water but dissolving in acetic ester to red to violet-blue solutions, and dyeing acetate artificial silk from a dye-bath containing these products in a fine dispersion red to violet-blue tints of good fastness properties. 7 I

12. The unsulfonated'azo-dyestufi of the formula I v which product is a dark powder insoluble in water, but dissolving in acetic ester to a red violet solution, and dyeing acetate artificial silk from a dye-bath containing thisproduct in a fine dispersion red violet tintsof good fastness properties.

13. The unsulfonated azo-dyestuff of the formula V i NOT- N=N N SOf-CH: on:

which product is a dark powder insoluble in water, but dissolving in acetic ester to a violet solu-' tion, and dyeing acetate artificial silk from a dye-bath containing this product in a fine dis persion violet tints of good fastness properties.

14. The unsulfonated azo-dye'stufi of the for.- mula V O-CH:

| OHa-GHr-OH which product is a dark powder insoluble in water, but dissolving in acetic ester to a violet solution, and dyeingacetate artificial silk from a dye-bath containing. this product ina fine dispersion violet tints of good fastness properties.

FRIEDRICH FELIX. WILHELM HUBER.

CHr-CHz-O-C Br 

